CH651749A5 - COMPOSITION FOR THE TREATMENT OF KERATINIC FIBERS BASED ON AMPHOTERIC POLYMERS AND CATIONIC POLYMERS. - Google Patents

Description

The present invention relates to new compositions, in particular cosmetic compositions, intended for use in the treatment of keratin fibers and in particular of the hair.

The present invention more particularly relates to the use, in combination with a cationic polymer, of an amphoteric polymer.

Cationic polymers have already been recommended for use in hair treatment compositions, in particular to facilitate the disentangling of the hair and to impart softness and suppleness to it.

These cationic polymers characterized by their substantivity, however, have the disadvantage of not giving sufficient hold and shine to the hair.

To remedy this drawback, the licensee has already proposed in the past to use anionic polymers with cationic polymers. Such an association is described in particular in French patent N ° 2383660.

The licensee noted, however, that, if the combination of an anionic polymer and a cationic polymer made it possible to confer remarkable cosmetic properties on the hair, it could nevertheless appear, after several successive applications to particularly damaged hair, some drawbacks such that a difficult disentangling, a rough character, sheathing and, in certain cases, static electricity.

The licensee has now discovered that by using an amphoteric polymer in place of anionic polymers, even particularly damaged keratin fibers, treated several times with the compositions, untangled perfectly, exhibited good resistance over time, without rough or sheathing, while being flexible, soft and non-electric and having more body and bulk.

More particularly interesting results have been noted for treatments usually followed by rinsing, such as shampoos, treatments using lotions or creams, used to obtain a hair conditioning effect, applied before or after. coloring, discoloration, shampoo or permanent.

The licensee discovered that the hair treated in this way was softer and more silky after several treatments than hair treated with anionic polymers combined with cationic polymers.

The main object of the invention therefore is a composition intended for use in the treatment of keratin fibers containing at least one cationic polymer and at least one amphoteric polymer. Another object of the invention consists of a process for treating keratin fibers using a cationic polymer and an amphoteric polymer.

The invention also relates to a process for fixing amphoteric polymers on keratin fibers using a cationic polymer.

Other objects will emerge from the description and examples which follow.

The compositions according to the present invention are essentially characterized in that they comprise, in an appropriate medium:

a) at least one amphoteric polymer comprising units A and B distributed statistically in the polymer chain where A denotes a unit deriving from a monomer comprising at least one basic nitrogen atom and B denotes a unit deriving from an acidic monomer comprising one or more carboxylic or sulfonic groups, or alternatively A and B may denote groups derived from zwitterionic monomers of carboxybetaine;

A and B can also denote a cationic polymer chain comprising secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group linked via a hydrocarbon radical, or alternatively A and B are part of a chain of a polymer with an ethylene unit a, ß-dicarboxylic acid, one of the carboxyl groups of which has been reacted with a polyamine comprising one or more primary or secondary amine groups, and b) at least a cationic polymer of the polyamine or poly- type

651,749

6

quaternary ammonium having amine or ammonium groups in the polymer chain or linked to it.

The amphoteric and cationic polymers used in accordance with the invention have a molecular weight of 500 to 2,000,000.

The amphoteric polymers corresponding to the definition indicated above which are more particularly preferred are chosen from the following polymers:

1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as more particularly acrylic acid, methacrylic acid, maleic acid, a-chloracrylic acid, and d 'a basic monomer derived from a substituted vinyl compound containing at least one basic nitrogen atom such as more particularly the dialkylaminoalkylmethacrylate and -acrylate, the dialkylaminoalkylmethacrylamide and -acrylamide. Such compounds are described in US Patent No. 3836537.

2) Polymers comprising units derived from:

a) at least one monomer chosen from acrylamides or methacrylamides substituted for nitrogen by an alkyl radical,

b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amino substituents of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylates with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tertiobutylacrylamide, N-tertiooctylacrylamide, N- octylacrylmide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides. The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric acids as well as alkyl monoesters having 1 to 4 carbon atoms of maleic acid or fumaric acid.

The preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, N-tert-butylaminoethyl methacrylates.

3) Crosslinked and alkylated polyaminoamides partially or totally derived from polyaminoamides of general formula:

-OC-

-R-

-NH — KCHA-NH-

where x = 2 and n = 2 or 3 or else x = 3 and n = 2,

this radical deriving from diethylenetriamine, triethylene-

tetramine or dipropylenetriamine;

2) in the proportions of 0 to 40 mol-% the radical II above, in which x = 2 and n = 1 and which is derived from ethylenediamine, or the radical:> ^

—N y N - derived from piperazine;

3) in the proportions of 0 to 20 mol-% the radical

—NH— (CH2) Ö — NH - derived from hexamethylenediamine,

these polyaminoamides being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives by means of 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide and alkylated by action acrylic acid, chloracetic acid or an alkanesultone or their salts.

The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms such as adipic acid, trimethyl-2,2,4- and 2,4,4-adipic, terephthalic, acids with ethylenic double bond , for example acrylic, metacrylic, itaconic acids.

The alkanesultones used in the alkylation are preferably propane- or butanesultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

4) Polymers comprising zwitterionic units of formula:

Ri-

"R2 C

.R,

R *

O

N®— (CH2) - C — 0e (III)

X Rs in which Ri denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacryl-amide group, x and y represent an integer from 1 to 3, R2 and R3 representing hydrogen, methyl, ethyl or propyl, R4 and R5 represents a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R4 and R5 does not exceed 10.

The polymers comprising such units may also contain units derived from non-zwitterionic monomers such as vinylpyrrolidone, dimethyl- or diethylaminoethyl acrylate or methacrylate or alkylacrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

5) Polymers derived from chitosan containing monomer units corresponding to the following formulas:

CHjOH

40

(I)

in which R represents a divalent radical derived from a saturated di-carboxylic acid, from an aliphatic mono- or dicarboxylic acid with an ethylenic double bond, from an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or of a radical derived from the addition of one of said acids with a bis-primary or bis-secondary amine, and Z denotes a radical of a bis-primary, mono- or bis-secondary polyalkylene polyamine and preferably represents:

1) in the proportions of 60 to 100 mol-%, the radical

(B)

50

NH

CO

R-COOH

(II)

in which the motif A is present in proportions of between 0 and 30%, B is present in proportions of between 5 and 50% and C is present in proportions of between 30 and 90%. In formula C, R represents a radical of formula:

R7 Rg

I I

R6-C- (0) n-CH

in which, if n = 0, R6, R, and R8, identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkyl-65 amine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfonic groups, an alkyl-thio residue in which the alkyl group carries an amino residue, at least one of the

7

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radicals R6, R7 and R8 being in this case a hydrogen atom; or n is equal to 1, in which case R6, R7 and R8 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

6) The polymers corresponding to general formula IV and described in French patent N ° 1400366:

r

(CH — CH2) -

CH CH

I I

COO H CO _ (IV)

i n r,

i r4 i n —r.,

I

r2

in which R represents a hydrogen atom, a ch30 radical, ch3ch20, phenyl, Rj denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R2 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R3 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: - R4 — N (R2) 2, R4 representing a group

-ch2-ch2-, -ch2-ch2-ch2-, -ch2-ch-

I

ch3

as well as the higher counterparts of these radicals and containing up to 6 carbon atoms.

7) Amphoteric polymers of the —A — Z — A — Z— type chosen from:

a) The polymers obtained by the action of chloracetic acid or sodium chloacetic on the compounds comprising at least one unit of formula:

-A-Z-A-Z-A- (V)

or A denotes a radical:

-N <^ y> N-

-N <^ ^> N-

where Z denotes B or B 'and at least once B'; B having the meaning indicated above and B 'is a bivalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising a or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more hydroxyl and / or carboxyl functions as well as the quaternary ammonium salts resulting from the reaction of chloracetic acid or sodium chloroacetate on polymers V. The preferred amphoteric polymers are those of groups 1, 2, 4, 5 and 6 defined above.

The cationic polymers more particularly preferred according to the invention are in particular:

a) Vinylpyrrolidone / acrylate or amino alcohol methacrylate copolymers (quaternized or not), such as those sold under the names Gafquat by Gaf Corp., for example Copoly-mother 845, Gafquat 734 or 755 described in particular in more detail in French Patent No. 2,077,143.

2) Derivatives of cellulose ethers comprising quaternary ammonium groups such as those described in French patent No. 1492597 and in particular the polymers sold under the names JR such as JR 125, JR 400 and JR 30 M and LR such as LR 400 and LR 30 M by the company Union Carbide Corp., cationic cellulose derivatives such as Celquat L 200 and Celquat H 60 sold by the company National Starch.

3) Quaternized Guar gum derivatives such as Jaguar C. 13 S sold by the company Celanese.

4) The cationic polymers chosen from the group formed by: a) the polymers of formula:

-a-z-a-z- (VI)

in which a denotes a radical comprising two amine functions and preferably:

35

40

in which Z denotes the symbol B or B ', B or B', identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain containing up to 7 carbon atoms in the main chain unsubstituted or substituted by hydroxyl groups and which may also contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the nitrogen and sulfur oxygen atoms being present in the form of an ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine group, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide , alcohol, ester and / or urethane.

b) The polymers of formula —A — Z — A — Z— (V) where A denotes a radical

-Nd>

NOT-

and z denotes the symbol B or B '; B and B ', identical or different, denote a bivalent radical which is an alkylene radical with a straight or branched chain, containing up to 7 carbon atoms in the main chain, unsubstituted or substituted by hydroxyl groups and which may also comprise oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of an ether or thioether, sulfoxide, sulfone, sulfonium, amine, alkylamine, alkenylamine, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcoholester group and / or urethane; these polymers and their preparation process are described in French patent N ° 2162025,

b) polymers of formula:

-a-zj-a-zj- (VII)

in which A denotes a radical comprising two amine functions and preferably:

-NOT

NOT-

and Zj denotes the symbol B] or B ', and it signifies at least once the symbol B'j; B! denotes a bivalent radical which is an alkylene or hydroxyalkylene radical with a straight or branched chain having up to 7 carbon atoms in the main chain, B \ is a biso valent radical which is a alkylene radical with a straight or branched chain having up to 7 carbon atoms in the main chain, unsubstituted or substituted by one or more hydroxyl radicals and interrupted by one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally having from 1 to 4 atoms and preferably 55 carbon atoms, optionally interrupted by an oxygen atom and optionally comprising one or more hydroxyl functions,

c) the alkylation products with alkyl and benzyl halides, tosylate or lower alkyl mesylate and the oxidation products of the polymers of formulas VI and VII above indicated under a and b.

The polymers of formula VII and their preparation process are described in French patent application No. 2280361. 5) Crosslinked polyaminoamides optionally alkylated 65 chosen from the group formed by at least one crosslinked polymer soluble in water, obtained by crosslinking of a polyaminopoly-amide A prepared by polycondensation of an acidic compound with a polyamine. The acid compound is chosen from: i) organic acids

651,749

des dicarboxylic, ii) aliphatic mono- and dicarboxylic acids with ethylenic double bond, iii) esters of the abovementioned acids, preferably esters of lower alkanols having from 1 to 6 carbon atoms, iv) mixtures of these compounds. The polyamine is chosen from bis-primary and mono- or bis-secondary polyalkylene polyamines. 0 to 40 mol-% of this polyamine can be replaced by a bis-primary amine, preferably ethylenediamine or by a bis-secondary amine, preferably piperazine, and 0 to 20 mol-% can be replaced by hexamethylenediamine. Crosslinking is carried out using a crosslinking agent B chosen from epihalohydrins, diepoxides, dianhydrides, unsaturated anhydrides, bis-unsaturated derivatives; crosslinking is characterized by the fact that it is carried out using 0.025 to 0.35 mol of crosslinking agent by amine group of the polyaminopoly-

amide A. These polymers and their preparation are described in more detail in French patent application No. 2252840.

This crosslinked polymer is perfectly soluble in water at 10% without gel formation, the viscosity of a 10% solution in water at 25 ° C is greater than 3 cPo and usually between 3 and 200 cPo.

The possible alkylation is carried out with glycidol, ethylene oxide, propylene oxide or acrylamide.

Crosslinked and optionally alkylated polyaminoamides do not contain a reactive group and have no alkylating properties and are chemically stable.

The polyaminoamides A themselves can also be used according to the invention.

6) The water-soluble crosslinked polyaminoamides obtained by the crosslinking of a polyaminoamide A described above by means of a crosslinking agent chosen from the group formed by:

I) The compounds chosen from the group formed by: 1) bis-halo-hydrines, 2) bis-azetidiniums, 3) bis-haloacylediamines, 4) bis-halides of alkyls;

II) the oligomers obtained by reaction of a compound chosen from the group formed by: 1) bis-halohydrins, 2) bis-azetidiniums, 3) bis-haloacyldiamines, 4) bis-halides of alkyls, 5) epihalohydrins, 6) diepoxides, 7) bis-unsaturated derivatives, with a compound b which is a bifunctional compound reactive with respect to compound a;

III) the quaternization product of a compound chosen from the group formed by compounds a and oligomers II and comprising one or more tertiary amine groups which can be alkylated totally or partially with an alkylating agent c preferably chosen from the group formed by chlorides , methyl or ethyl bromides, iodides, sulfates, mesylates and tosylates, benzyl chloride or bromide, ethylene oxide, propylene oxide and glycidol, crosslinking being carried out using 0.025 to 0.35 mol, in particular from 0.025 to 0.2 mol and more particularly from 0.025 to 0.1 mol of crosslinking agent by amine group of the polyaminoamide.

These crosslinkers and these polymers as well as their preparation process are described in French application No. 2368508 incorporated in the description by reference.

7) Derivatives of water-soluble polyaminoamides resulting from the condensation of a polyalkylene polyamine with a polycarboxylic acid, followed by alkylation by bifunctional agents such as the adipic acid / dialkoyl-aminohydroxyalkyl / dialkoylene triamine copolymers in which the alkyl radical contains 1 to 4 carbon atoms and preferably denotes methyl, ethyl, propyl, described in French patent No. 1583363.

The compounds making it possible to obtain interesting results are the adipic acid / dimethylaminohydroxypropyl / di-ethylenetriamine copolymers sold under the name Cartaretine F, F4 or F8 by the company Sandoz.

8) The polymers obtained by reaction of a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid, and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid being between 0.8: 1 and 1.4: 1; the resulting polyamide being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyamide of between 0.5: 1 and 1.8: 1, cited in EUA patents Nos. 3227615 and 2961347 incorporated by reference.

Particularly interesting polymers are those sold under the name Hercosett 57 by the company Hercules Incorpo-rated having a viscosity at 25 ° C of 30 cPo at 10% in aqueous solution; under the name PD 170 or Delsette 101 by the company Hercules in the case of the copolymer of adipic acid / epoxy-propyl / diethylenetriamine.

9) Water-soluble cyclopolymers having a molecular weight of 20,000 to 3,000,000 such as homopolymers comprising, as main constituent of the chain, units corresponding to formula VIII or VIII ':

(viii) -

ch2 r "c

I

/VS\

shout

h, c ch2

\ /

not

/ e \

r r '

(vim-

ch,

ch.

-r "c ncr"

I I

h2c ch,

\ /

n I

r in which R "denotes hydrogen or methyl, R and R 'denote, independently of one another, an alkyl group having from 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 with 5 carbon atoms, a lower amidoalkyl group and where R and R 'can denote, jointly with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl or morpholinyl, as well as the copolymers comprising units of formula VIII or VTII 'and, preferably, acrylamide or diaceton-acrylamide derivatives, Y "is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate.

Among the quaternary ammonium polymers of the type defined above, those which are more particularly preferred are the homopolymer of dimethyldiallylammonium chloride sold under the name Merquat 100 having a molecular weight of less than 100,000 and the chloride chloride copolymer dimethyldiallylammonium and acrylamide having a molecular weight greater than 500,000 and sold under the name Merquat 550 by the company Merck.

These polymers are described in French patent N ° 2080759 and its certificate of addtion N ° 2190406.

10) The quaternary polyammoniums of formula:

rRj

NOT-

I ®

R2 Xe

R,

-NOT-

©

I

R4 Xe n

(IX)

where Rj, R2, R3 and R4, equal or different, represent aliphatic, alicyclic or arylaliphatic radicals containing a maximum of 20 carbon atoms or lower hydroxyaliphatic radicals, or alternatively Raet R2 and R3 and R4, together or 60 separately, constitute, with the nitrogen atoms to which they are attached, heterocycles possibly containing a second hetero atom other than nitrogen, or else Rj, R2, R3 and R4 represent a group:

R'3 denoting hydrogen or lower alkyl

/

R ',

—CH, —CH

\

R'4 designating - CN

R'4

9

651,749

0

R ',

o o

-C-N

—C — 0R'S; —C — R's

/

\

R ',

0

II

-C — O —R'7 — D;

o

11

- C — NH — R ', - D

R's denoting lower alkyl, R'6 denoting hydrogen or lower alkyl, R'7 denoting alkylene, D denoting a quaternary ammonium group. A and B may represent polymethylenic groups containing from 2 to 20 carbon atoms, which may be linear or branched, saturated or unsaturated and which may contain, intercalated in the main chain, one or more aromatic rings such as the group:

2375853, 2388614, 2454547, 3206462, 2261002 and 2271378 incorporated by reference.

Other polymers of this type are described in US Patents Nos. 3874870, 4001432, 3929990, 3966904, 4005193, 4025617, 4025627, 4025653, 4026945 and 4027020 incorporated in this specification by reference.

11) Homopolymers or copolymers derived from acrylic or methacrylic acid and comprising as motif:

r,

i

-ch, c-

-ch,

-ch-0-ch *

C = 0

have

r.

i

-c— i c = o

-ch,

one or more —CH2 —Y — CH2 groups, with Y denoting o, s, so, so2,

R's, O

I 11

-S-S-, -N-, SN- Xf, -CH-, -NH-C-NH-,

I I I

R's R'9 OH

O O

He II

—C-N or -C-O-

i

R's with X] ~ designating an anion derived from a mineral or organic acid, R'8 designating hydrogen or lower alkyl, R'9 designating lower alkyl, or A and Rj and R3 form, with the two nitrogen atoms to which they are attached, a piperazine cycle; in addition, if A denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B can also denote a group:

- (CH2) „CO-D-OC- (CH2)„, in which —D denotes:

a) a glycol residue of formula —O — Z — O— where Z denotes a linear or branched hydrocarbon radical or a group corresponding to the formulas:

not

/ \

u R.

0

1

have

R2 Ns i

r3

-R „R2

10th r.

i

-vs

1

c = o i

NH i a xe i

- Do not R4 (X)

i r3

- [ch2-ch2-ol ch2 — ch2 -

or ch, -ch-o

CH.,

CH2-CH-

i y CH3

where x and y denote an integer from 1 to 4 representing a defined and unique degree of polymerization or any monomer from 1 to 4 representing an average degree of polymerization;

b) a bis-secondary diamine residue such as a piperazine derivative of formula:

-NOT

NOT-

c) a bis-primary diamine residue of formula:

—NH — Y — NH— where Y denotes a linear or branched hydrocarbon radical or the bivalent radical -CH2-CH2-S-S-CH2-CH2-,

d) a ureylene group of formula - NH —CO — NH -; - N is such that the molecular mass is between 1000 and 100,000, X ~ denotes an anion.

Polymers of this type are described, in particular, in French patents Nos 2320330 and 2270846, French applications Nos 76.20261 and 2336434 and US Patents Nos 2273780,

20 in which R, is H or CH3,

A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms,

R2, R3, R4, identical or different, are an alkyl group, having 1 to 18 carbon atoms, benzyl,

25 R5, R6 = H or alkyl having 1 to 6 carbon atoms,

X denotes methosulfate, halogen such as chlorine, bromine.

The comonomer (s) which can be used belong to the family: acrylamide, methacrylamide, diacetonacrylamide, acrylamide and methacrylamide substituted with nitrogen by lower alkyls, alkyl esters of acrylic and methacrylic acids, vinylpyrrolidone, vinyl esters.

By way of example, we can cite:

- the copolymers of acrylamide and of P-methacryloyloxyethyltri-methylammoniummethosulfate sold under the names

35 Reten 205, 210, 220 and 240 by Hercules,

- the copolymers of ethyl methacrylate, oleyl methacrylate, p-methacryloyloxydiethylmethylammoniummethosulfate referenced under the name of Quaternium 38 in the “Cosmetic Ingredient Dictio-nary”,

40 - the copolymer of ethyl methacrylate, abietyl methacrylate and P-methacryloyloxydiethylmethylammoniummethosulfate referenced under the name of Quaternium 37 in the “Cosmetic Ingredient Dictionary”,

- the polymer of p-methacryloyloxyethyltrimethylammonium-

45 bromide referenced as Quaternium 49 in the “Cosmetic Ingredient Dictionary”,

- the copolymer of P-methacryloyloxyethylmethylammonium-methosulfate and p-methacryloyloxystearyldimethylammonium-methosulfate referenced under the name of Quaternium 42 in the “Cosso metic Ingredient Dictionary”,

- the aminoethylacrylatephosphate / acrylate copolymer sold under the name Catrex by the company National Starch, which has a viscosity of 700 cPo at 25 ° C. in an 18% aqueous solution,

- grafted and crosslinked cationic copolymers having a molecular weight of 10,000 to 1,000,000 and preferably from 15,000 to

500,000 resulting from the copolymerization:

a) at least one cosmetic monomer,

b) dimethylaminoethyl methacrylate,

c) polyethylene glycol, and

D) a polyunsaturated crosslinker,

described in French patent N ° 2189434 incorporated by reference.

The crosslinker is taken from the group consisting of: ethylene glycol dimethacrylate, diallyl phthalates, divinyl benzenes, tetraalyloxyethane and polyallylsucroses having from 2 to 65 5 allyl groups per mole of sucrose.

The cosmetic monomer can be of a very varied type, for example a vinyl ester of an acid having from 2 to 18 carbon atoms, an allyl or methallyl ester of an acid having from 2 to

651,749

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18 carbon atoms, an acrylate or methacrylate of a saturated alcohol having from 1 to 18 carbon atoms, an alkylvinyl ether whose alkyl radical has from 2 to 18 carbon atoms, an olefin having from 4 to 18 carbon atoms, a vinyl heterocyclic derivative, a dialkyl or N, N-dialkylaminoalkyl maleate in which the alkyl radicals have from 1 to 3 carbon atoms or an unsaturated acid anhydride.

Polyethylene glycol has a molecular weight between 200 and several million and preferably between 300 and 30,000.

These grafted and crosslinked copolymers preferably consist of:

a) from 3 to 95% by weight of at least one cosmetic monomer chosen from the group consisting of: vinyl acetate, vinyl propionate, methyl methacrylate, stearyl methacrylate, lauryl methacrylate, l ethyl vinyl ether, cetylvinyl ether, stearyl vinyl ether, hexene-1, octadecene-1, N-vinylpyrroIidone and N, N-diethylaminoethyl monomaleate, maleic anhydride and diethyl maleate;

b) from 3 to 95% by weight of dimethylaminoethyl methacrylate,

c) from 2 to 50% by weight and preferably from 5 to 30% of polyethylene glycol,

d) from 0.01 to 8% by weight of a crosslinker as defined above, the percentage of the crosslinker being expressed relative to the total weight of a + b 4- c.

Other cationic polymers which can be used are polyalkylenimines and in particular polyethylenimines, polymers containing vinylpyridine or vinylpyridinium units in the chain, polyamine and epichlorohydrin condensates, quaternary polyureylenes, chitosan derivatives.

The compositions preferred for the purpose of the present invention are compositions containing, as amphoteric polymer, a crosslinked and alkylated polyaminoamide as defined in group 3 of the amphoteric polymers described above and, as cationic polymer, crosslinked and optionally alkylated polyaminoamides or polyaminoamide derivatives as defined in groups 5, 6, 7,9 and 10 of the cationic polymers described above.

Another composition giving particularly advantageous results comprises polymers comprising units derived from at least one monomer chosen from acrylamides or methacrylamides substituted for nitrogen by an alkyl radical and from at least one acidic comonomer containing one or more groups reactive carboxyls as defined in group 2 of amphoteric polymers and cyclopolymers and quaternary polyammoniums of groups 9 and 10 of cationic polymers.

Among these compositions, those giving particularly notable results are those comprising the amphoteric polymer called PAM-2 with the cationic polymer PAA-1 or Cartarine-Fine, or else the amphoteric polymer sold under the name Amphomer with cationic polymers called PAQ-1 or PAQ-3.

The polymers used according to the invention may be present in the compositions in proportions varying between 0.01 and 10% by weight, preferably in proportions of between 0.5 and 5% by weight. The pH of these compositions is generally between 2 and 11 and preferably between 3 and 10 and in particular between 4 and 8.5.

The compositions in accordance with the invention preferably do not contain other polymers, and in particular no anionic polymer.

These compositions can be in various forms such as liquid, cream, emulsions, gel, etc. They can contain, in addition to water, any cosmetically acceptable solvent chosen in particular from monoalcohols such as alkanols having between 1 and 8 carbon atoms such as ethanol, isopropanol, benzyl alcohol, alcohol. phenylethyl; polyalcohols such as alkylene glycols such as ethylene glycol, propylene glycol, glycol ethers such as mono-, di- and triethylene glycolmonoalkyl ethers, for example ethylene glycolmonoethyl ether, ethylene glycolmono-

ethyl ether, diethylene glycol monoethyl ether, used alone or as a mixture. These solvents are present in proportions less than or equal to 70% by weight, relative to the weight of the total composition.

These compositions can also contain electrolytes and, among these, those which are more particularly preferred are the alkali metal salts such as the sodium, potassium or lithium salts. These salts are preferably chosen from halides such as chloride, bromide, sulfates or the salts of organic acids such as in particular acetates or lactates.

These compositions can be in powder form, to be diluted before use.

The compositions whose usual applications are followed by rinsing are preferred and give the most surprising results.

They can be in particular in the form of shampoo, rinse-off lotion, cream or treatment product which can be applied before or after coloring or discoloration, before or after shampooing, before or after a perm and can also take the form of coloring products, styling lotions, brushing lotions, bleaching products, perms, relaxers.

A preferred embodiment is constituted by the use in the form of shampoo. In this case, the compositions according to the invention contain, in addition to the abovementioned polymers, at least one anionic, nonionic, cationic or amphoteric surfactant or their mixtures.

Among the anionic surfactants that may be mentioned in particular the following compounds as well as their mixture: the alkali salts, the ammonium salts, the amine salts or the amino alcohol salts of the following compounds:

- alkylsulphates, alkylethersulphates, alkylamidesulphates and ethersulphates, alkylarylpolyethersulphates, monoglyceridesulphates;

- alkyl sulfonates, alkyllamidesulfonates, alkylarylsulfonates, α-olefinsulfonates;

- alkyl sulfosuccinates, alkyl ethers sulfosuccinates, alkyl amidesulfosuccinates;

- alkyl sulfosuccinamates;

- alkyl sulfoacetates, alkyl polyglycerolcarboxylates;

- alkylphosphates, alkyl etherphosphates;

- alkylsarcosinates, alkylpolypeptidates, alkyllamidopoly-peptidates, alkylisethionates, alkylltaurates,

the alkyl radical of all these compounds being a linear chain of 12 to 18 carbon atoms;

- fatty acids such as oleic, ricinoleic, palmitic, stearic acid, coconut oil or hydrogenated coconut oil acids, carboxylic acids of polyglycolic ethers corresponding to the formula:

Alk - (OCH2 - CH2) „- OCH2 - C02H where the substituent Alk corresponds to a straight chain having 12 to 18 carbon atoms and where n is an integer between 5 and 15.

Among the anionic surfactants, those which are more particularly preferred are sodium, ammonium or tri-ethanolamine lauryl sulphates, oxyethylenated sodium lauryl ether sulphate with 2.2 mol of ethylene oxide, the acid triethanolamine salt lauroylkérati-nique, the triethanolamine salts of the condensation product of coconut acids and animal protein hydrolysates, the products of formula:

R - (OCH2 - CH2) s - OCH2 - COOH in which R is an alkyl radical generally from C12 to C14 and x varies from 6 to 10.

Among the nonionic surfactants which can optionally be used in admixture with the above-mentioned anionic surfactants, mention may be made of the condensation products of a monoalcohol, an α-diol, an alkylphenol, an amide or a diglycolamide with glycidol such as for example the compounds corresponding to the formula:

5

10

15

20

25

30

35

40

45

50

55

60

65

11

651,749

Ri —CHOH —GHz — O - (CH ;, —CHOH —GHz — 0) p — H

in which R4 denotes an aliphatic, cycloaliphatic or arylaliphatic radical preferably having between 7 and 21 carbon atoms and their mixtures, the aliphatic chains possibly comprising ether, thioether or hydroxymethylene groups and where p represents an average statistical value between 1 and 10 included, as described in French Patent No. 2091516; compounds corresponding to the formula:

rso — e-c2:30 - (ch2ohhi- h in which R5 denotes an alkyl, alkenyl or alkylaryl radical and q is an average statistical value between 1 and 10 inclusive as described in French patent No. 1477048; compounds corresponding to the formula:

r6conh - ch2 - ch2 - o - ch2 - ch2 -

O —i-CH2CHOH-CH2-CHr- H

in which R6 denotes a radical or a mixture of linear or branched, saturated or unsaturated aliphatic radicals which may optionally comprise one or more hydroxyl groups,

having 8 to 30 carbon atoms, of natural or synthetic origin, r represents an integer or decimal from 1 to 5 and denotes the average degree of condensation, as described in French patent application No. 2328763.

Other compounds belonging to this class are alcohols, alkylphenols, fatty acids with linear fatty chains containing 8 to 18 polyethoxylated or polyglycerolated carbon atoms. Mention may also be made of copolymers of ethylene and propylene oxides, condensates of ethylene and propylene oxides on fatty alcohols, polyethoxylated fatty amides, polyethoxylated fatty amines, ethanolamides, esters of glycol fatty acid, fatty acid esters of sorbitol, fatty acid esters of sucrose.

Among these nonionic surfactants, those which are more particularly preferred correspond to the formula:

r4 — choh — ch2 — o— (ch2 — choh - ch2 - 0) p h where R4 denotes a mixture of alkyl radicals having 9 to 12 carbon atoms and p has a statistical value of 3.5;

R5-0 - [- C2H3O (CH2OH) 4j-H where Rs denotes C12H25 and q has a statistical value of 4 to 5;

r6-conh-ch2-ch2-o-ch2-ch2-o-

[CH2CHOH — CH2O- ^ H

where R <j denotes a mixture of radicals derived from lauric, myristic, oleic and copra acids and r has a statistical value of 3 to 4.

The preferred polyethoxylated or polyglycerolated fatty alcohols are oleic oxyethylenated alcohol with 10 mol of ethylene oxide, lauric oxyethylenated alcohol with 12 mol of ethylene oxide, nonylphenol oxyethylenated with 9 mol of ethylene oxide , poly-glycerolated oleic alcohol with 4 mol of glycerol and polyoxyethylenated sorbitan monolaurate with 20 mol of ethylene oxide.

Among the cationic surfactants which can be used alone or as a mixture, mention may in particular be made of fatty amine salts such as alkylamine acetates, quaternary ammonium salts such as chloride, alkyl dimethylbenzyl bromide ammonium, alkyltrimethylammonium, alkyldimethylhydroxy-ethylammonium, dimethyldistearylammonium, alkylaminoethyltrimethylammonium methosulfates, alkylpyridinium salts, imidazoline derivatives. The alkyl radicals in these compounds preferably have between 1 and 22 carbon atoms. Mention may also be made of compounds of a cationic nature, such as amine oxides such as alkoyldimethylamine oxides or alkylaminoethyldimethylamine oxides.

Among the amphoteric surfactants which can be used, mention may more particularly be made of alkylamino, mono- and dipropionates, betaines such as N-alkylbetaines, N-alkyl-sulfobetaines, N-alkyllaminobetaines, cyclo-imidiniums like alkyllimidazolines, derivatives of asparagine. The alkyl group in these surfactants preferably denotes a group having between 1 and 22 carbon atoms.

- In these shampoos, the concentration of surfactant is generally between 3 and 50% by weight and preferably between 3 and 20%, the pH is generally between 3 and 10.

Another preferred embodiment consists of the use of rinse-off lotions to be applied mainly before or after shampooing. These lotions can be aqueous or hydroalcoholic solutions, emulsions, thickened lotions or gels.

When the compositions are in the form of emulsions, they can be nonionic or anionic. The nonionic emulsions consist mainly of a mixture of oil and / or fatty alcohol, and of polyethoxylated alcohol such as stearyl alcohols or polyethoxylated cetylstearyl alcohols. Cationic surfactants such as those defined above can be added to these compositions.

Anionic emulsions are mainly made from soap.

When the compositions are in the form of thickened lotions or gels, they contain thickeners in the presence or absence of solvents. The thickeners that can be used can be sodium alginate or gum arabic or cellulose derivatives such as methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose. Thickening of lotions can also be obtained by mixing polyethylene glycol and polyethylene glycol stearate or distearate or by mixing phosphoric ester and amide. The thickener concentration can vary from 0.5 to 30% by weight and preferably from 0.5 to 15% by weight. The pH of lotions to rinse varies essentially between 3 and 9.

When the compositions according to the invention are in the form of styling lotions, shaping lotions, or so-called styling lotions, these lotions generally comprise, in aqueous, alcoholic or hydroalcoholic solution, the components of the combination above defined as well as possibly nonionic polymers and anti-foaming agents.

When the compositions of the present invention constitute dye compositions for keratin fibers, they contain, in addition to (or) amphoteric polymer (s) and (or) cationic po-lymer (s), at least oxidation dye precursor and / or a direct dye and optionally various adjuvants allowing their presentation in the form of the cream, gel or solution described above.

They can also contain antioxidant agents, sequestrants or any other adjuvant usually used in this type of composition.

The oxidation dye precursors are aromatic compounds of the diaminobenzene or diaminopyridine, amino-phenol or phenol type. Among these precursors there are, on the one hand, the precursors of dyes of the “para” type and the precursors of dyes of the “ortho” type chosen from diaminobenzenes, diamino-pyridines, aminophenols and diphenylamines and, on the other hand, the couplers which are “meta” derivatives chosen from metadiamino-benzenes, metadiaminopyridines, metaaminophenols, metadiphenols, phenols, naphthols.

Among the direct dyes, mention may be made of azo dyes, anthraquinone dyes, nitro derivatives of the benzene series, inda-mines, indophenols, indoanilines.

The pH of these dye compositions is generally between 7 and 11 and it can be adjusted to the desired value by adding an alkalizing agent such as ammonia, hydroxides alca5

10

15

20

25

30

35

40

45

50

55

60

65

651749

12

lin, alkali and ammonium carbonates, alkylamines, alkanolamines or a mixture thereof.

The combination according to the invention can finally be carried out in compositions intended for waving or straightening the hair. This composition contains, in addition to the amphoteric polymer (s) and the cationic polymer (s), one or more reducing agents and possibly other adjuvants usually used in this type of composition. and is used in conjunction with a neutralizing composition.

The reducing agents are chosen from sulphites, mercaptants and more particularly from thioglycolates or thiolactates or their mixture.

The neutralizing composition contains an oxidant chosen from hydrogen peroxide, alkali bromates or perborates.

The above compositions can also be pressurized as an aerosol; carbon dioxide, nitrogen, nitrous oxide, volatile hydrocarbons such as butane, isobutane, propane or preferably chlorinated or fluorinated hydrocarbons can be used as propellant.

The compositions according to the invention may contain any other ingredient usually used in cosmetics, such as perfumes, dyes which may have the function of coloring the composition itself, preserving agents, electrolytes, sequestering agents, thickening agents. , softening agents, synergists, foam stabilizers, sun filters, peptizing agents, depending on the intended application.

The process for treating keratin fibers according to the invention may consist in applying the composition containing the above-defined amphoteric polymer and the cationic polymer directly to the hair, in particular by shampooing, coloring the hair, to a perm or to conditioning of the hair using the above-mentioned compositions.

The combination according to the invention can also be formed in situ on the hair by first applying a composition, for example in the form of a prelotion, containing the cationic polymer and, secondly, a composition such as for example a shampoo, a dye containing the amphoteric polymer.

According to another variant of the invention, a shampoo containing the cationic polymer <10 can be applied first and secondly a composition such as a lotion containing the amphoteric polymer.

One can proceed by successively using a composition for perming, straightening, coloring or bleaching containing the cationic polymer, followed by a composition containing the amphoteric polymer, the latter being present in a composition which may be a shampoo. , an oxidizing solution, a simple lotion.

One can also proceed by successively using a first shampoo containing the cationic polymer in a first step and in a second step a second shampoo containing the amphoteric polymer, the pHs of the compositions applied in these two times can be different and adjusted so to be at the time of application of the composition containing the amphoteric polymer under conditions allowing good deposition of the combination according to the invention on the hair.

The invention also relates to a method for curling or straightening the hair and consists in firstly applying a reducing composition containing the cationic polymer / amphoteric polymer association, and secondly the neutralizing composition.

According to a variant, the reducing composition containing the cationic polymer (s) can be applied in a first step, and in a second step the neutralizing composition containing the amphoteric polymer (s).

The present invention can also be defined as a process for fixing amphoteric polymers on keratin fibers, characterized in that one causes the fixation of the amphoteric polymer by associating it with a cationic polymer present either in the same composition or applied to the prior to keratin fibers.

The following examples are intended to illustrate the invention without however limiting it.

In the examples which follow, the amounts are expressed by weight of active material.

Example 1:

The following composition is prepared:

Amphoteric polymer called AZAM-1 0.8 g

Cationic polymer called Onamer M 0.4 g

Maypon 4 CT 8 g

Surfactant called AES 1 g

Sodium chloride 3 g

Sodium hydroxide q.s.p. pH 8.7

Water q.s.p. 100g

This composition is used as a shampoo.

We impregnate dirty and wet hair and note the formation of a soft foam. After rinsing wet hair detangles well.

Dried hair is characterized by its nervousness and especially by its swelling and its maintenance.

Other examples 2 to 8 of shampoo according to the invention are illustrated in table 1. As for example 1, good detangling of wet hair is observed and the dried hair is nervous, swelling and has good hold.

Table I Shampoos

Example

Polymer

Solvents and / or

%

pH

Acidifier or

No.

Amphoteric

%

Cationic

%

Surfactant

%

alkalizing additives

2

AZAM-2

0.7

PAQ-3

0.6

TA.2

Lipoproteol LCO

8 7

Sodium chloride

1

8

Hydrochloric acid

3

PAM-1

0.7

Kytex H

0.5

Miranol C2 M TA.l

5 10

4

Hydrochloric acid

4

Amphomer

0.3

PAQ-1

0.4

TA.2

12

Sodium chloride

5

5.6

Hydrochloric acid

5

Amphomer

0.4

Gafquat 755

0.2

TA.l

12

6.3

Hydrochloric acid

13

651,749

Example

Polymer

Solvents and / or

%

pH

Acidifier or

No.

Amphoteric

%

Cationic

%

Surfactant

%

alkalizing additives

6

Amphomer

0.4

PAA-1

0.5

ALE 12 Miranol C2 M

5 7

Sodium chloride

5

6

Hydrochloric acid

7

Amphomer

0.3

PAQ-2

0.5

Sandopan DTC-AC Miranol C2 M

8 4

Sodium chloride

4

8.5

Welded

8

Amphomer

0.2

Cartaretin F.4

0.7

Triethanolamine lauryl sulfate

25

Coconut Diet Amide

2

8

Lactic acid

Example 2:

The following composition is prepared:

Amphoteric polymer called PAM-3 0.4 g

Cationic polymer called PAA-R 0.5 g2o

Non-ionic surfactant called TA-1 0.5 g

Hydrochloric acid q.s.p. pH 8

Water q.s.p. 100g

This composition is used for rinsing the hair.

This composition is applied to washed and towel-dried hair.

After a few minutes of application, rinse.

Wet hair is easily disentangled. Dry hair is plump and the hairstyle is good.

Similar results are obtained by applying, under the same conditions as in Example 9 above, the compositions of Examples 10 to 20 of Table II.

Table II (Rinsed Lotions)

Example No.

Polymer

Solvents and / or adjuvants

%

pH

Acidifier or alkalizer

Amphoteric

%

Cationic

%

Surfactant

%

10

Amphomer

0.7

Onamer m

0.5

Cetyl stearyl alcohol Polawax GP200 Cellosize QP 4400 H Ammonyx 27

2

3

0.5 1.5

5.7

Lactic acid

11

Amphomer

0.75

PAA-1

0.6

Lexein X.250

0.5

8.8

Hydrochloric acid

12

PAM-2

0.6

PAQ-3

0.8

Cetyl stearyl alcohol Polawax GP200 Cellosize QP 4400 H Lexein X.250 Ammonyx 27

2

3

0.7

0.8 2

5

Hydrochloric acid

13

PAM-2

2

Onamer m

0.9

7

Lactic acid

14

PAM-2

0.9

JR400

0.7

4

Hydrochloric acid

15

AZAM-1

1.5

Gafquat 755

2

3.5

Hydrochloric acid

16

AZAM-1

0.1

PAQ-2

0.05

Lexein X.250

0.1

3.5

Hydrochloric acid

17

AM

0.8

PAQ-3

0.46

Lexein X.250

1.6

5

Hydrochloric acid

18

AM

1.5

PAA-1

0.62

Lexein S.620

1.1

8.6

Hydrochloric acid

19

CHIT

3

PAQ-3

5

ACS 15 OE

3

Cetyl alcohol Ammonyx 27

6 2

7.3

Hydrochloric acid

20

CHIT

0.06

JR 400

0.15

3.2

Hydrochloric acid

651749

14

By applying the compositions of Examples 17, 18 and 20 in the form of styling lotion without rinsing, it is observed that the hairstyle remains in good condition and that the hair has a soft feel.

Examples of “two-step” formulas

Example 21:

An aqueous lotion having the following composition is first applied:

Cartaretine F4 0.6 g

Cellosize QP 4400 H 0.5 g

Water q.s.p. 100 g pH 7 (per HCl)

After an exposure time of a few minutes, an aqueous lotion having the following composition is applied in the second step: Amphomer 1.2 g

Cellosize QP 4400 H 0.4 g

Water q.s.p. 100 g pH 8.1 (per HCl)

Example 22:

First, a shampoo having the following composition is applied:

Merquat 100 0.5 g

Surfactant called TA-1 9 g

Water q.s.p. 100 g pH 8.6 (by HCl) An aqueous lotion having the following composition is applied in a second step:

Polymer called PAM-2 0.3 g

Cellosize QP 4400 H 0.4 g

Water q.s.p. 100 g pH 7 (per HCl)

Example 23:

The following composition A is prepared:

PAM-2 1.0 g

Orthooxyquinoline neutral sulfate 0.05 g 70% hydrogen peroxide q.s.p. 20 volumes

Hydrochloric acid q.s.p. pH 2

Water q.s.p. 100 g 40 g of this composition are mixed before use with 40 g of the following composition B1:

Nonylphenol 4 mol ethylene oxide 19.0 g

Nonylphenol 9 mol ethylene oxide 17.0 g

Coconut diethanolamide 14.0 g

Propylene glycol 10.0 g

Ethyl alcohol 3.5 g

PAQ 4 2.0 g

Ethylenediaminotetracetic acid 1.0 g

Ammonia 22 ° B 10 ml

Water q.s.p. 100 g A creamy gel is obtained. Apply to dark brown hair. After 30 to 45 minutes of laying, rinse.

The hair is then dark blond.

Example 24:

The following composition A is prepared:

PAM-2 1.0 g

Orthooxyquinoline neutral sulfate 0.05 g

Hydrogen peroxide q.s.p. 20 volumes

Hydrochloric acid q.s.p. pH 2

Water q.s.p. 100 g This composition is mixed before use with the following composition B2:

Nonylphenolpolyoxyethylenated 19.0g (to 4 mol of ethylene oxide)

Nonylphenolpolyoxyethylenated to 9 mol of ethylene oxide PAQ 4

Ethyl alcohol s Propylene glycol

Ammonia at 22 ° B Coconut diethanolamide Metadiaminoanisol sulfate Resorcinol io Metaaminophenol base Paraaminophenol base Nitro paraphenylenediamine Ethylenediaminetetracetic acid Sodium bisulfite d = 1.32 15 Water q.s.p.

17.0 g 2.0 g 3.5 g 10.0 g 10 ml 14.0 g 0.03 g 0.40 g 0.15 g 0.087 g 1.00 g 3.00 g 1.20 g 100 g

50 g of this formula are mixed in a bowl with the same amount of composition A and the gel obtained is applied to the hair with a brush.

Leave on for 30 min and rinse.

20 The hair is easily detangled, the feel is silky. We do the styling and dry.

The hair is shiny, nervous, it has body, volume, the touch is silky and easy disentangling.

On a brown background we get a chestnut shade.

25

Example 25:

The following compositions are prepared:

a) Reducing composition

Thioglycolic acid 6.0 g

30 Ammonia q.s.p. pH 9.5

Sequestering agent 0.2 g

Merquat 100 2.0 g

Perfume 0.5 g

Water q.s.p. 100 ml

35

b) Fixing liquid

Potassium bromate 9.5 g

Amphomer 1.0 g

Tartaric acid pH 6.5 Colorant Fragrance

Water q.s.p. 100 g On sensitized hair, the reducing liquid is very easily applied and penetrates deeply into the hair.

After rinsing and application of the fixing liquid, a very regular crimping is observed.

After drying, the hairstyle is particularly good.

Example 26:

n / a The following compositions are prepared:

a) Reducing composition

Ammonium sulfite 4.0 g

Ammonium bisulphite 3.3 g

Monoethanolamine 3.9 g

55 Onamer M 2.0 g Nonylphenolpolyoxyethylenated with 9 mol of ethylene oxide 0.5 g

Perfume 0.5 g

Water q.s.p. 100 ml 60 b) Fixing liquid

Potassium bromate 9.5 g

PAM-2 1.0 g

Tartaric acid pH 6.5 Perfume 65 Colorant

Water q.s.p. 100 g On sensitized hair, the reducing liquid is very easily applied and penetrates deeply into the hair.

15

651,749

After rinsing and application of the fixing liquid, a very regular crimping is observed.

After drying, the content of the hairstyle is particularly good.

In the examples above, the trade names and the 5 abbreviations used denote the following products:

PAM-1: polymer resulting from the reaction of the polymer PAA-1 with propanesultone in proportions of 50%.

PAA-1: polyaminoamide resulting from the polycondensation of adipic acid and diethylenetriamine in equimolar amounts io and crosslinked with epichlohydrin at the rate of 11 mol of crosslinker for 100 amino groups of the polyaminoamide.

PAM-2: polymer resulting from the alkylation of the polymer PAA-1 with sodium chloroacetate.

AZAM-1: polymer obtained by polycondensation of epichlorohydrin and piperazine in the presence of sodium hydroxide and betainized.

AZAM-2: mixed polycondensate of epichlorohydrin and of a mixture (piperazine + sodium glycolate) in molar proportions 60/40.

Polyamphoteric motif: - A — CH2 —CHOH — CH2— 20

C1CH, - CHOH - CH,

N-CH2CHOH — CH2 — jr-Cl

PAQ-1: polymer of formula ch3 ch3

I I

n + (ch2) 3 n + ch2 - conh - (ch2) 2 -nh - co - ch2

I I

_ch3c1- ch3ci-

A designating either - N or - N-

O-

PAQ-2: polymer of formula

~ CH3 I

-N + (CH2) 3-

PAQ-3: polymer of formula "ch3 o ch3 I

-n + -

- (CH2) 6

ch, cr ch3

CH,

COONa

AMPHOMER: copolymer of octylacrylamide / acrylate / butyl-aminoethylmethacrylate sold under the name Amphomer by the company National Starch.

AM: polymer of formula

"CH3 I

O

30

CH-CH2-CH - CH-

/

COOH CO-NH- (CH2) 3-N ^

c2h5

40

PAM-3: polymer resulting from the alkylation of the PAA-1 polymer with propanesultone.

CHIT: polymer with patterns

CH, OH

nh

I

co I

ch, -ch2-cooh n® - (ch2) 3 -nh-c-nh - (ch2) 3 -n® - (ch2) 2 - o - (ch2) 2

I I

_ch3c1® ch3ci-

n being equal to approximately 6.

KYTEX H: partially deacetylated chitin sold by the company Hercules.

GAFQUAT 755: quaternary polyvinylpyrrolidone copolymer having a PM of 1,000,000 sold by the company General Aniline.

CARTARETINE F.4: adipic acid / dimethyl-aminohydroxypropyldiethylentriamine copolymer sold by the company Sandoz.

ONAMER M: poly (dimethylbutenylammonium chloride) a- (ù (triethanolammonium chloride) sold by the company Onyx Chemical Co.

JR 400: polymer of hydroxyethylcellulose and epichlorohydrin quaternized with trimethylamine sold by the company Union Carbide.

MERQUAT 100: homopolymer of dimethyl-dialkylammonium chloride with a molecular weight of less than 100,000 sold by the company Merck.

MA YPON 4 CT: triethanolamine salt of the condensation product of coconut acid and animal protein hydrolyzate sold by the company Stepan.

AES: Alkoyl (C12-C14) oxyethylenated sodium ether sulfate with 2.2 mol of ethylene oxide.

TA-1: nonionic surfactant of formula:

RCHOH - CH20 —h CH2 - CHOH - CH20 -fcr- H

R = C9-C12 alkyl

n = 3.5 mean statistical value.

TA-2: nonionic surfactant of formula:

C12H2

ch2oh H 1 o.

/ h oh

-0-CH, -CH-

CH, OH

OH

nh2

in the proportions of about 50/50.

PAAR-R: polyaminoamide resulting from the polycondensation of adipic acid and diethylentriamine in equimolar amounts and crosslinked with a random oligomer crosslinking agent of formula:

n = 4.2 mean statistical value.

FTA 12: lauryl alcohol polyethoxylated with 12 mol of ethylene oxide.

LIPOPROTÉOL LCO: mixed sodium and triethanolamine salts and lipoamino acids obtained by combination of lauric acid with amino acids from the total hydrolysis of collagen sold by Rhône-Poulenc.

MIRANOL C.2M: cycloimidazolinic derivative of coconut oil sold by the company Miranol

651,749

16

c „h2

NOT

nc

I X

CH,

, CH, —COONa s CH, - CH, - O - CH, - COCT

\ /

ch2

SANDOPANDTC.AC: trideceth-7 carboxylic acid of formula:

CH3 (CH2) n -CH2 - (OCH2 -CH2) 6OCH2-COOH sold by the company Sandoz.

POLAWAX GP 200: mixture of fatty alcohols and oxy-ethylene products sold by the company Croda.

CELLOSIZE QP 4400 H: 2% viscosity hydroxyethylcellulose in aqueous solution, from 4400 Cps at 25 ° C at Brookfield module 4.

AMMONYX 27: monoalkyltrimethylammonium chloride sold by the company Franconyx.

Alkyl = tallow radical.

LEXEIN X.250: hydrolyzate of proteins derived from Collagen sold by the company Wilson.

LEXEIN S 620: potassium salt of a condensate of collagen protein and coconut fatty acid, of molecular weight 700-800 sold by the company Inolex.

A CS 15 OE: oxyethylenated cetylstearyl alcohol containing 15 mol of ethylene oxide.

PAQ-4: polymer of formula:

C4H5

• n + - I

C4H

ch3

(ch2) 3 — n + -Br- I '4fip ch3

- (ch2) 4-Br ~

R

Claims (20)

651749 1) vinylpyrrolidone / acrylate or methacrylate copolymers of amino alcohol, quaternized or not, 1) Copolymers of a monomer of a vinyl compound carrying a carboxylic group preferably chosen from acrylic acid, methacrylic acid, maleic acid, α-chloracrylic acid, and of a basic monomer d 'a substituted vinyl compound containing at least one basic nitrogen atom preferably chosen from dialkylaminoalkylmethacrylates or acrylates, dialkylaminoalkylmethylcrylamides and acrylamides. 1. Composition intended to be used for the treatment of keratin fibers and in particular of the hair, characterized in that it comprises, in an appropriate medium allowing the application of the polymers to the keratin fibers: a) at least one amphoteric polymer comprising units A and B distributed statistically in the polymer chain where A denotes a unit of a monomer comprising at least one basic nitrogen atom and B denotes a unit of an acidic monomer comprising one or several carboxylic or sulphonic groups, or else A and B can denote groups of zwitterionic monomers of carboxybetaine; A and B can also denote a cationic polymer chain comprising secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulfonic group that is linked via a hydrocarbon radical, or well A and B form part of a chain of a polymer with ethylene units a, ß-dicarboxyls one of whose amido-amino groups comprises one or more primary or secondary amine groups, and b) at least one cationic polymer of polyamine or poly quaternary ammonium type comprising amine or ammonium groups in the polymer chain or linked to it. 2 nffl r., (X) I R3 X® wherein Ri is H or CH3; A is a linear or branched alkyl group of 1 to 6 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R2, R3, R4, identical or different, denote an alkyl group, having 1 to 18 carbon atoms or a 40 benzyl group; R5, R „denote H, alkyl having 1 to 6 carbon atoms; X ~ denotes a methosulfate or halide anion. 2) cellulose ether derivatives comprising quaternary ammonium groups, 2) Polymers comprising units a) of at least one monomer chosen from acrylamides or methacrylamides substituted for nitrogen by an alkyl radical, b) at least one acidic comonomer containing one or more reactive carboxylic groups, and c) at least one basic comonomer such as esters with primary, secondary, tertiary and quaternary amino substituents of acrylic and methacrylic acids and the quaternization product of Dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate. 2. Composition according to claim 1, characterized in that the amphoteric polymer is chosen from: 2 3) quaternized Guar gum derivatives, 3. Composition according to one of claims 1 or 2, characterized in that the cationic polymer is chosen from: 3 651,749 dant to the formula R4 — N (R2) 2, R * representing a group -ch, -ch2-, -ch2-ch2-ch, -, -ch2-ch- I ch3 as well as the higher counterparts of these radicals and containing up to 6 carbon atoms. 3) Crosslinked and partially or totally alkylated poylaminoamides of polyaminoamide of general formula: -OC- -R- -CO- -z-h- Ri- • R, R, R * O N @__ (CH2) - C —oe Rs in which Rx denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamine or methacrylamide group, x and y represent an integer from 1 to 3, R2 and R3 represent hydrogen, methyl, ethyl or propyl, R4 and R5 represent a hydrogen atom or an alkyl radical in such a way that the sum of the carbon atoms in R4 and R5 does not exceed 10. 4. Composition according to one of claims 1 to 3, characterized in that the polymers are each present in propor- 50 tions from 0.1 to 10% by weight. ^ '4 O -CH one or more groupings - CH2 S, SO, so2, R'o - Y — CH2 with Y denoting O, O -S-S-, -N-, ®N- Xf, -CH-, -NH-C-NH-, I I I R's R's OH O O He II C-N or -C-O- I R's with Xf denoting an anion of a mineral or organic acid, R's denoting hydrogen or lower alkyl, R'9 denoting lower alkyl, or A and Ra and R3 form, with the two atoms to which they are attached, a piperazine ring; in addition, if A denotes a linear or branched, saturated or unsaturated alkylene, hydroxyalkylene radical, B can also designate a group: - (CH2) „-CO-D-OC- (CH2)„ in which - D denotes: a) a glycol residue of formula —O — Z — O— where Z denotes a linear or branched hydrocarbon radical or a group corresponding to the formulas: - [CH2 - CH2—0] „CH2 — CH2 - CH, —CH — O CH, -CH, -CH- CH, where x and y denote an integer from 1 to 4 representing a defined and unique degree of polymerization or any number from 1 to 4 representing an average degree of polymerization; b) a bis-secondary diamine residue such as a piperazine derivative of formula: -not NOT- c) a bis-primary diamine residue of formula: 15 -NH-Y-NH- where Y denotes a linear or branched hydrocarbon-based radical or the bivalent radical - CH2 — CH2 — S - S — CH2 — CH2—, d) a ureylene group of formula - NH — CO — NH—; - n is such that the molecular mass is between 1000 and 20,100,000. X ~ denotes an anion. 4 4) the cationic polymers chosen from the polymers of formula —A — Z — A — Z— (VI), in which A denotes a radical comprising two amine functions, and preferably: -N <^ ^> N- and Z denotes the symbol B or B '; B and B ', identical or different, denoting a linear or branched alkylene radical unsubstituted or substituted by hydroxyl groups and which can additionally contain oxygen, nitrogen, sulfur atoms, 1 to 3 aromatic rings and / or heterocyclic, polymers of formula: —A — Zj - A — Zj - (VII) in which A has the same meaning as above and Zj denotes the symbol Bj or B '] and signifies at least once B'i, Bj being a linear or branched alkylene or hydroxyalkylene radical B'j is a linear or branched alkylene radical unsubstituted or substituted by one or more hydroxyl radicals and interrupted by one or more nitrogen atoms, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and optionally comprising one or more 4) Polymers comprising zwitterionic units of formula: CH, OH - ° | o (AT) (b) NHCOCHj CHjOH NH, (vs) in which the motif A is present in proportions of between 0 and 30%, B is present in proportions of between 5 and 50% and C is present in proportions of between 30 and 90%; in formula C, R represents the radical of formula Ri Rs R6 — C— (0) n CH I I in which n is equal to 0, in which case R6, R7 and Rs, identical or different, each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monoalkylamine residue or a dialkylamine residue optionally interrupted by one or several nitrogen atoms and / or optionally substituted by one or more amine, hydroxyl, carboxyl, alkylthio, sulfoniac groups, an alkylthio residue in which the alkyl group carries an amino residue, at least one of the radicals Rö, R7 and Rs being in this case a hydrogen atom, or else n is equal to 1, in which case R6, R7 and R8 each represent a hydrogen atom, as well as the salts formed by these compounds with bases or acids. 5 651749 5. Composition according to claim 1, characterized in that the amphoteric polymer is a polyaminoamide as defined in 3 in claim 2 and that the cationic polymer is chosen from polyaminoamide derivatives of groups 5, 6, 7, 9 and 55 10 of claim 3. 5) polyaminoamides, 5 hydroxyl functions; polymers of formula (VI) or (VII) alkylated with lower alkyl or benzyl hylides, tosylate or lower alkyl mesylate, 5) Chitosan polymers containing monomer units corresponding to the following formulas: 40 (I) in which R represents a divalent residue of a saturated dicarboxylic acid, of an aliphatic mono- or dicarboxylic acid having an ethylenic double bond, of an ester of a lower alkanol having 1 to 6 carbon atoms with these acids or of a radical comprising a motif of said acids and the remainder of a bis-primary or bis-secondary amine, and Z denotes a radical of a bis-prirriary, mono- or bis-secondary polyalkylene polyamine, these polyaminoamides being crosslinked by radicals of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis-unsaturated derivatives, in an amount of 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide and alkylated with acid residues acrylic, chloroacetic or an alkanesultone or their salts. 6. Composition according to claim 1, characterized in that the amphoteric polymer is a polymer as defined in group 2 of claim 2 and that the cationic polymer is a polymer as defined in group 9 or 10 of claim 3. 60 7. Composition according to claim 1, characterized in that the amphoteric polymer is a polycondensate of adipic acid and diethylenetriamine in equimolecular amount, crosslinked by epichlorohydrin radicals and comprising on one or more nitrogen atoms a methylcarboxylate unit sodium, and by the fact that the 65 cationic polymer is a polycondensate of adipic acid and diethylenetriamine in equimolecular quantity and crosslinked by epichlorohydrin radicals or an adipic acid / dimethylaminohydroxypropyldiethylenediamine copolymer. 6) crosslinked polyaminoamides chosen from: io a) crosslinked polyaminoamides, alkylated or not, water-soluble, which are polycondensates of an acidic compound with a polyamine, these polycondensates being crosslinked by radicals of a crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, unsaturated anhydrides, bis-unsaturated derivatives 6) The polymers corresponding to the general formula (IV): 55 R (CH CH2) - CH CH- I I COOH CO I not - • R, (IV) (III) 65 R4 I N R3 I R * in which R represents a hydrogen atom, a CH30 radical, CH3CH20, phenyl, Rj denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R2 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R3 denotes a lower alkyl radical such as methyl, ethyl or a radical 7) polymers which are polycondensates comprising units of a polyalkylene polyamine comprising two groups 40 primary amine and at least one secondary amine group and dicarboxylic acid units chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having 3 to 8 carbon atoms, the carbon ratio, the molar ratio between the polyalkylene polyamine and the dicarboxylic acid being between 45 0.8: 1 and 1.4: 1, and the epichlorohydrin units in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyamide of between 0.5: 1 and 1.8: 1. 7) Amphoteric polymers of type —A —Z —A —Z— chosen from: a) polymers comprising at least one unit of formula: —A — Z — A — Z—, where A denotes -NOT not- and in which Z denotes the symbol B or B '; B or B ', identical or different, denoting a straight or branched chain alkylene radical containing up to 7 carbon atoms in the main chain which is unsubstituted or substituted by hydroxyl groups and which may also contain oxygen atoms, d 'nitrogen, sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of an ether, thioether, sulfoxide, sulfone, sulfonium, alkylamine, alkenylamine group, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide, alcohol, ester and / or urethane, and comprising on the nitrogen atom of the group A and when Z comprises an amine function, carboxymethyl or methylcarboxylate units, b) polymers of formula A —Z — A — Z (V), where A denotes a radical: -NOT <d> N ~ where Z denotes B or B 'and at least once B'; B having the meaning indicated above and B 'is a bivalent straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or not by one or more hydroxyl radicals and comprising one or more atoms nitrogen, the nitrogen atom being substituted by an alkyl chain optionally interrupted by an oxygen atom and necessarily having one or more hydroxyl and / or carboxyl functions as well as the quaternary ammonium salts of chloracetic acid or of sodium chloracetate with the polymers (V). 8. Composition according to claim 1, characterized in that the amphoteric polymer is an octylacrylamid-acrylate / butylaminoethylmethacrylate copolymer and that the cationic polymer is chosen from the polymers of formula: ch3 o ch3 I II I N— (CH2) 3 — NH — C — NH— (CH2) 3 - N— (CH2) 2 — O— (CH2) 2 - | - n I I CH® Cl® CH® Cl® ch3 ch3 I I n- (ch2) 3-n ch2-conh- (ch2) 2- I I CH? Cl® CH? CL® ■ NH-CO-CH2 8) Homopolymers comprising, as main constituent of the chain, units corresponding to formula (VIII) or (VIII '): s »r cw, (vili) - ["ch2 r" c (wine -) - | -ch2 I I h2c ch2 \ / \ / n n / ® \ r r ' ye in which R "denotes hydrogen or methyl, R and R 'denote, independently of one another, an alkyl group having 1 to 60 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group and where R and R 'denote, together with the nitrogen atom to which they are attached, heterocyclic groups such as piperidinyl or morpholinyl, as well 65 that the copolymers comprising units of formula (VIII) or (VIII ′) and, preferably, acrylamide or diacetone acrylamide derivatives, Y e is an anion, such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. ch 2 -r "c \; r" - I I h2c ch2 651,749 9. Composition according to one of claims 1 to 8, characterized in that the pH is between 2 and 11. 9) The quaternary polyammoniums of formula (IX): "Ri n- R, Xe R, -NOT- R4 Xe n (IX) where R! and R2, R3 and R4, equal or different, represent aliphatic, alicyclic or arylaliphatic radicals containing a maximum of 20 carbon atoms or lower hydroxyaliphatic radicals, or else R! R2 and R3 and R4, together or separately, constitute with the nitrogen atoms to which they are attached, heterocycles possibly containing a second hetero atom other than nitrogen, or else Rls R2, R3 and R4 represent a group: , R'3 R'3 denoting hydrogen or lower alkoxyl / - CH2 - CH R'4 designating - CN 10. Composition according to one of claims 1 to 9, characterized in that it contains at least one solvent chosen from monoalcohols, polyalcohols, glycol ethers. 20 10) Homopolymers or copolymers derived from acrylic or methacrylic acid and comprising as motif: O R'6 II Il / —C — O —R'7 — D; O O -C-N; It II \ O - C — OR'5; —C — R's R's II -C-NH-R'7-D R's denoting lower alkyl, R'6 denoting hydrogen or lower alkyl, R'7 denoting alkylene, D denoting a quaternary ammonium group, A and B can represent polymethylenic groups containing from 2 to 20 carbon atoms, which can be linear or branched, saturated or unsaturated and which may contain, inserted in the main chain, one or more aromatic rings such as the group: -ch, 30 35 R, I -this c = I o NOT / \ Re Rfi -CH, r. I -VS I c = o a I -Noah -ch, I r3 Xe r, i -vs- I c = o I NH I HAVE 11. Composition according to one of claims 1 to 10, characterized in that it contains at least one anionic, cationic, nonionic or amphoteric surfactant or their mixture. 11) Polyalkylenimines. 12. Composition according to one of claims 1 to 11, characterized in that it is in the form of an aqueous, alcoholic or hydroalcoholic solution, a gel, a thickened lotion, an emulsion , cream or powder. 12) Polymers containing vinyl-pyridine or vinylpyridinium units in the chain. 45 13) The condensates of polyamines and epichlorohydrin. 13. Composition according to one of claims 1 to 12, characterized in that it contains cosmetically acceptable ingredients chosen from perfumes, dyes which can have the function of coloring the composition itself or the fibers treated, preservatives, sequestering agents, thickening agents, softening agents, synergists, foam stabilizers, sun filters, peptizing agents depending on the application envisaged. 35 14. Composition according to one of claims 1 to 13, characterized in that the composition contains at least one electrolyte. 14) Quaternary polyuretylenes. 15. Composition according to one of claims 1 to 14, intended to be used for dyeing keratin fibers, characterized in that it comprises, in addition to the polymers, at least one oxidation dye precursor 40 and / or a direct dye. 15) Derivatives of chi tosane. In the proportion of between 0.025 and 0.35 mol per amine group of the polyaminoamide; b) crosslinked water-soluble polyaminoamides which are polycondensates of an acidic compound with a polyamine, these polycondensates being crosslinked by radicals of a crosslinking agent 20 chosen from: I) bis-halohydrins, bis-azetidiniums, bis-halo-acylediamines, alkyl bis-halides, II) oligomers which are condensates of group I compounds or epihalohydrins, diepoxides, bis- - derivatives 25 unsaturated, with a bifunctional compound reactive with respect to these compounds, III) a quaternized product comprising units of group I compounds and group II oligomers with tertiary amino groups which can be totally or partially alkylated with a 30 alkylating agent, these polyaminoamides being crosslinked in an amount of 0.025 to 0.35 mol of crosslinking agent per amine group of the polyaminoamide, c) derivatives of water-soluble polyaminoamides which are polycondensates of a polyalkylene polyamine with an acid 35 polycarboxylic, these polycondensates being alkylated by residues of bifunctional agents which are adipic acid / dialkoylaminohydroxyalkylldialcoylene triamine copolymers, 16. Composition according to one of claims 1 to 14, intended to be used for waving or straightening the hair, characterized in that it contains, in addition to the polymers, one or more reducing agents. 45 17. Process for treating keratin fibers, characterized in that at least one composition according to one of claims 1 to 14 is applied to said fibers. 18. The method of claim 17, characterized in that the application is followed by rinsing after a sufficient exposure time 50 to impregnate the hair. 19. The method of claim 17, characterized in that one applies, in a first step, a composition containing a cationic polymer as defined in one of claims 1 or 3 and, in a second step, a composition containing the amphoteric polymer as defined in one of claims 1 or 2. 20. The treatment method as claimed in claim 17, intended for curling or straightening the hair, characterized in that the reducing composition containing a cationic polymer and optionally an amphoteric polymer is applied, and 60 in a second time, the neutralizing composition containing the amphoteric polymer when the latter is not present in the composition applied in the first time.